It is well-known in the rubber industry that preferred accelerators are those which, when mixed into vulcanizable rubber compositions and heated, exhibit an induction period (scorch delay) prior to the onset of vulcanization. It is also preferred that vulcanization proceed rapidly once the induction period has ended. Such a combination of characteristics has the practical benefits of maximum processing safety and shorter cure cycles. The present invention provides novel accelerator systems which meet these preferred criteria and also provides processes by which such preferred accelerator characteristics may be attained.
The sulfinyl benzothiazoles of the present invention may be prepared by adaptations of prior art procedures, wherein a 2-(alkylthio)-benzothiazole is first synthesized, then oxidized to its sulfinyl analog. The alkylthio benzothiazoles can be obtained by reaction of an alkali metal salt of 2-mercaptobenzothiazole with an alkyl halide as described in the following publications.
A. F. Halasa and G. E. P. Smith, Jr., J. Org. Chem., 36 636 (1971). PA0 C. G. Moore, J. Chem. Soc., 4237 (1952). PA0 W. A. Sexton, J. Chem. Soc., 470 (1939). PA0 V. F. Kucherov, Zhur Obshchei Khim., 19, 752 (1949) Chem. Abstr., 44, 3488f (1950). PA0 2-(isopropylsulfinyl)-benzothiazole PA0 2-(sec-butylsulfinyl)-benzothiazole PA0 2-(n-butylsulfinyl)-benzothiazole PA0 2-(t-butylsulfinyl)-benzothiazole PA0 2-(cyclohexylsulfinyl)-benzothiazole PA0 2-(2'-carbomethoxyethylsulfinyl)-benzothiazole PA0 2-(methylsulfinyl)-benzothiazole PA0 2-(benzylsulfinyl)-benzothiazole PA0 2-(2'-dodecylsulfinyl)-benzothiazole PA0 2-(2'-tridecylsulfinyl)-benzothiazole PA0 2-(2',4',4'-trimethyl-2'-pentylsulfinyl)-benzothiazole
Alternatively, 2-(alkylthio)-benzothiazoles have been prepared by reaction of an alkali metal alkyl mercaptide with 2-chlorobenzothiazole, c.f., P. E. Todesco and P. Vivarelli, Boll. Sci. Fac. Chim. Ind. Bologna, 20, 125 (1962), Chem. Abstr., 59, 8562d (1963). The addition of 2-mercaptobenzothiazole to butene-1, butene-2, heptene-1 and heptene-3, catalyzed by BF.sub.3 etherate, has been used to prepare the corresponding secondary alkylthio benzothiazoles, c.f., A. N. Bezumnova and N. K. Rozhkova, Khim.Geterotsikl. Soedin., Sb., 1971, No. 3; Chem. Abstr. 78, 43342r (1973). This paper also discloses the preparation of 2-(tert.butylthio)-benzothiazole by reaction of 2-mercaptobenzothiazole with isobutylene in 80 percent sulfuric acid.
The Todesco et al reference describes the preparation of 2-(methylsulfinyl)-benzothiazole by oxidation of the methylthio analog with peroxybenzoic acid. The preparations of 2-(alkylsulfinyl)-6-nitro-benzothiazoles by simultaneous oxidation/nitration with HNO.sub.3 /H.sub.2 SO.sub.4 have been reported, c.f. Ger. Offen. 2,400,419 (7/17/75); Chem. Abstr., 83, 179039h (1975).
In a report by A. E. Wood and E. G. Travis [J. Am. Chem. Soc., 50, 1226 (1928)], a procedure is disclosed which uses aqueous sodium hypochlorite of "low alkalinity" to convert n-heptylsulfide to the sulfinyl analog in unspecified yield and purity. Other procedures are also known to be generally applicable for oxidation of thioethers to their sulfinyl analogs, c.f. S. R. Sandler and W. Karo, "Organic Functional Group Preparations," Chapter 19, Academic Press, New York and London, 1968.